EP3308956B1 - Plaque thermo-déformable - Google Patents

Plaque thermo-déformable Download PDF

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Publication number
EP3308956B1
EP3308956B1 EP16194022.6A EP16194022A EP3308956B1 EP 3308956 B1 EP3308956 B1 EP 3308956B1 EP 16194022 A EP16194022 A EP 16194022A EP 3308956 B1 EP3308956 B1 EP 3308956B1
Authority
EP
European Patent Office
Prior art keywords
plate
thermally
component
film
plastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16194022.6A
Other languages
German (de)
English (en)
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EP3308956A1 (fr
Inventor
Manfred Oberkofler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Senoplast Klepsch and Co GmbH
Original Assignee
Senoplast Klepsch and Co GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to ES16194022T priority Critical patent/ES2894109T3/es
Application filed by Senoplast Klepsch and Co GmbH filed Critical Senoplast Klepsch and Co GmbH
Priority to EP16194022.6A priority patent/EP3308956B1/fr
Priority to CA3039141A priority patent/CA3039141A1/fr
Priority to BR112019007442A priority patent/BR112019007442A2/pt
Priority to MX2019004313A priority patent/MX2019004313A/es
Priority to CN201780063595.7A priority patent/CN109843582B/zh
Priority to JP2019520619A priority patent/JP6871368B2/ja
Priority to KR1020197010661A priority patent/KR102268281B1/ko
Priority to US16/339,108 priority patent/US20210283824A1/en
Priority to RU2019114209A priority patent/RU2745957C2/ru
Priority to PCT/EP2017/076197 priority patent/WO2018069502A1/fr
Publication of EP3308956A1 publication Critical patent/EP3308956A1/fr
Application granted granted Critical
Publication of EP3308956B1 publication Critical patent/EP3308956B1/fr
Active legal-status Critical Current
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft

Definitions

  • the invention relates to a thermally deformable plate or film and a method for producing such a plate or film.
  • the invention further relates to a thermally deformed plate and various applications of such plates.
  • Thermally deformable sheets are used in numerous areas of application, such as in the automotive industry for body parts for cars, trucks, caravans, construction machinery, commercial vehicles, in the sanitary area for bathtubs or shower trays, in the furniture industry as furniture films, in the construction industry, for E&E housings, for Leisure and sports equipment or in the rail and aircraft industry. While such panels are extremely easy to process, they do not achieve the properties that are often required in the respective area of application. In particular, the mechanical and physico-chemical properties such as scratch resistance and chemical resistance, e.g. for automotive applications, are often insufficient.
  • EP1723194 discloses a radiation-curable composite layered sheet or film composed of at least one substrate layer and a cover layer which contains a radiation-curable composition with a glass transition temperature below 50 ° C. with a high double bond density, a process for its production and its use.
  • DE19917965 discloses radiation-curable composite sheet or film made of at least one substrate layer and a cover layer, characterized in that the cover layer consists of a radiation-curable material with a glass transition temperature above 40 ° C.
  • a third approach according to the prior art is what is known as two-component injection molding ("2K injection molding").
  • 2K injection molding a liquid multi-component reactive system is introduced into the cavity of the mold of the injection molding machine in an injection molding machine and the coating is evenly distributed over the surface of the molded part in the subsequent embossing step.
  • the coating is cured in the mold so that the component can be removed from the mold.
  • the paint is cured by means of UV radiation.
  • This process provides very scratch-resistant surfaces, but it is extremely cost-intensive, can only be used for small-area components and is also unsuitable for shaded areas. Application to automobile bodies is difficult to implement within a reasonable budget.
  • the object of the present invention is therefore to provide a thermally deformable plate or film in which these disadvantages do not occur.
  • thermoly deformable plate or film comprising a thermoplastic plastic plate or plastic film and a lacquer top layer with at least two components arranged thereon, characterized in that the lacquer top layer has an already hardened but still thermoformable component as the first component and as the second component has a thermally curable component.
  • Such a plate or film can be provided directly from the manufacturer of the thermoplastic plastic plate or plastic film by applying a lacquer which can be hardened in two stages to the thermoplastic plastic plate or plastic film.
  • the first stage of hardening takes place e.g. at the manufacturer of the thermoplastic plastic sheet or plastic film, while the second stage - the final hardening of the paint - takes place at the location of the thermoforming process, at the same time as the thermoforming process.
  • top coat of paint is not to be understood as two separate layers, each with one of the two components. Rather, the top coat of paint is so too understand that the two components of the top coat of paint are mixed or blended with one another.
  • the paint When applying to the plastic film or plate, the paint is still liquid.
  • the first component is then hardened.
  • the hardened first component is thermoformable, i.e. the first component can be reversibly deformed when exposed to temperature and pressure.
  • the top layer of lacquer is so hard that the plates or foils can be stored and stacked or such a plate or foil can be thermoformed without impairing the optical properties and surface quality, in particular the gloss.
  • the top coat of paint is not yet fully cured or fully cured.
  • the lacquer top layer preferably has a chemical resistance to acetone of less than 5 minutes.
  • the top coat of paint has a chemical resistance to acetone of over 5 minutes.
  • thermoformable component be cured to allow thermoforming. Originally when the top coat of paint was applied, the first component or the components of the first component were still liquid and not hardened.
  • the second component of the lacquer top layer preferably cures completely when the sheet or film is thermoformed. If necessary, a slight, preferably thermal, post-curing may also be necessary. Hardening is understood to be the process in which the polymerisation process starts as a result of the polymerisation of the monomers and oligomers in the lacquer top layer, so that the hardness of the lacquer top layer increases.
  • Thermally deformable plate or film is understood to mean that the plate or film can be deformed by the action of pressure and temperature. During this deformation, the second component of the top coat of paint hardens.
  • the thermally deformable plate or film can also be thermoplastically deformable.
  • the invention relates to a method for producing a thermally deformable film or plate.
  • Areas of application for such sheets or foils include, for example, the automotive, rail and aircraft industries; the furniture industry; the construction industry; the sanitary area; Freetime and sports.
  • the exterior area such as body parts for cars, trucks, caravans, construction machinery, commercial vehicles such as roof modules, decorative panels, bumpers, trunk covers, full-surface body parts or the interior area such as panels, decorative panels, moldings, displays , functional control units etc. into consideration.
  • furniture foils, furniture parts and the like can be named as examples.
  • sanitary area z. B. to mention bathtubs or shower trays.
  • films can be used as housings in all areas of industry, for suitcases or device housings, etc. or in the construction industry, for E&E housings, for leisure and sports equipment.
  • the mechanical and physico-chemical properties such as scratch resistance, chemical resistance, for example for automotive applications, are often inadequate in the prior art, so that there is a great need for films or plates according to the invention.
  • film or plastic film and plate or plastic plate are used synonymously in the context of the patent application and films and plates are meant equally, even if only film or plate is mentioned.
  • thermoplastic plastic sheet or film represents the carrier for the top coat of paint and it is thermally deformable.
  • the thermoplastic plastic film can be designed in one or more layers. In the case of a multilayer thermoplastic plastic sheet or film, this is preferably a coextrudate.
  • the plastic sheet or film is preferably a flat multilayer composite body which comprises a substrate layer and at least one further layer.
  • thermoplastic materials such as thermoplastic polymers are used as the main component for the thermoplastic plastic sheet or film.
  • a thermoplastic material is understood to be a plastic that can be thermoplastically deformed in a certain temperature range.
  • the thermoplastic deformability is a reversible process, so that the thermoplastic material can be repeated as often as desired by cooling and warming up to the deformable state.
  • Thermoplastic materials include pure plastics (homopolymers, hetero- or copolymers) and plastic blends (mixtures of different plastics).
  • Polyolefins, styrene polymers, polycarbonate (PC), polyacrylates, polyesters, etc. can be named as thermoplastic materials.
  • polyolefins for example, polyethylene or polypropylene can be mentioned.
  • styrene polymers for example acrylonitrile-butadiene-styrene terpolymers (ABS), polystyrene (PS), impact modified polystyrene (HI-PS), acrylonitrile-styrene-acrylic ester (ASA), other copolymers comprising styrene units can be mentioned.
  • thermoplastic materials can be, for example, thermoplastic elastomers (TPE), thermoplastic elastomers based on olefins (TPO) or thermoplastic polyurethane (TPU).
  • thermoplastic material there can also be a blend of plastics as thermoplastic material or it can be necessary to add additional substances in order to achieve the desired properties.
  • ABS / PMMA or ABS / PC for example, can be named as blends of the aforementioned plastics.
  • thermoplastic plastic sheet or film is multilayered, the individual layers can also contain the aforementioned polymers.
  • the lacquer layer is then applied to the upper layer of the plastic film (e.g. PMMA).
  • the layers can contain regrind, recycled material or regrind (e.g. from previous production steps or the adjustment of the extrusion system or the edge trimming). Colorants and / or UV additives can also be added.
  • Matting agents can also be added, which are generally understood to mean additives which influence the surface of a coating in such a way that its degree of gloss is reduced. Usually associated with this is an increase in surface roughness, which in the subsequent process, lamination, shows improved processing behavior.
  • Suitable matting agents are known to the person skilled in the art and include, for example, inorganic fillers, in particular silica or crosslinked polymers in bead form (“polymer beads”), preferably acrylate beads. The amount added is preferably between 0.1% by weight and 5% by weight.
  • Colorants are pigments, dyes or effect pigments. In contrast to dyes, pigments are insoluble in the carrier medium.
  • the carrier medium is the substance into which the pigment is incorporated, for example a lacquer or a plastic. Dyes and pigments together belong to the colorants and can be inorganic or organic, colored or achromatic.
  • UV additives can be added.
  • UV absorbers lead to an absorption of the UV radiation, which passes through the polymer and convert it into thermal energy. UV stabilizers inhibit the free radicals that are created by exposure to UV radiation and stop further decomposition.
  • the thickness of the substrate layer is preferably between 50 ⁇ m and 5 mm. Any additional layers preferably have a thickness between 5 ⁇ m and 1 mm.
  • Lacquer top layer
  • the paint for the top coat of paint is originally a multi-component paint (at least a two-component paint) or a paint containing at least two components that cure differently.
  • the first component is already cured in the finished product (the thermally deformable sheet or film).
  • the first component in the paint is a component that can be hardened by means of UV light, i.e. in the finished product a component that is hardened by means of UV light.
  • Possible components that can be hardened by means of UV light can contain, for example, acrylate oligomers such as urethane (meth) acrylate oligomers, such as Laromer® UA 9072 from BASF.
  • acrylate oligomers such as urethane (meth) acrylate oligomers, such as Laromer® UA 9072 from BASF.
  • Other ingredients are reactive thinners, photoinitiators, optionally defoamers and UV additives.
  • the UV light-curable component comprises acrylate oligomers, preferably urethane (meth) acrylate oligomers, reactive diluents and photoinitiators.
  • Photoinitiators are chemical compounds that are subject to photolysis after exposure to UV light and form reactive species such as radicals and can initiate polymerization.
  • Reactive thinners are substances that reduce the viscosity of the paint and become part of the paint through copolymerization when the paint is subsequently hardened. For example, epoxies, styrene or acrylates are possible.
  • UV light is understood to mean radiation with a wavelength in the range from approx. 380 nm to 10 nm.
  • the formulation In contrast to conventional two-component paint systems, the formulation has no pot life.
  • the thermally curable component preferably comprises blocked (or blocked) isocyanates and polyols.
  • a blocked isocyanate is an addition compound of a highly reactive isocyanate, e.g. with alcohols ("urethanes") or with amines ("ureas"). At higher temperatures, these isocyanates are then released again in order to then enter into the polymerization reaction with the polyols as reactants.
  • Aromatic polyester polyols such as Terol 250 ® polyol from Huntsman, can be mentioned as polyols.
  • the top coat of paint is produced by applying the paint to the substrate and partially curing it. Partial curing only affects the first component and not the second component.
  • UV additives UV absorbers and UV stabilizers
  • the materials and colorants used in the layers below are protected from UV radiation, which increases the color stability and the consistent material properties is significantly improved over the period of use when irradiated with UV light.
  • the top layer or the UV lacquer can be transparent or can be made with different colorants.
  • the lacquer layer can also contain nanoparticles to improve various properties.
  • the paint is preferably essentially free from solvents, since solvents are environmentally unfriendly. Solvent-based paints also have other disadvantages, which result, for example, from the fact that the evaporation of the paint can result in fluctuations in the thickness of the paint layer.
  • the lacquer top layer can have a glossy or matt finish.
  • the blocked isocyanate is preferably one that is between 140 ° C and 210 ° C, preferably 160 ° C to 190 ° C ° C, particularly preferably between 165 ° C and 185 ° C ° C releases the isocyanate.
  • aromatic isocyanates for example monomeric diphenyl methane diisocyanates
  • aliphatic isocyanates for example isophorone diisocyanate
  • suitable Additives such as blocking agents can be used to set the temperature at which the second component cures.
  • the lacquer must be thermoformable before the second component is thermally cured. After the thermal curing (i.e. after the curing of the second component as well), the lacquer can still be thermoplastic deformable, but it can also be designed to be thermoset.
  • protective films of this type are usually made of polyethylene or PET, they can have an adhesive layer on the back.
  • the thickness of the cover layer is preferably between 1 ⁇ m and 100 ⁇ m, preferably about 5 to 20 ⁇ m.
  • the mixing ratio between the first component and the second component is preferably between 3: 1 and 1: 3 by mass.
  • Thermally curable components include all ingredients that are required for thermal curing, while UV-curable components include all ingredients that cure using UV light.
  • One advantage of the invention is that either the subsequent painting or UV curing step is not required.
  • the stacking strength of the plate with the partially cured lacquer layer is also advantageous compared to the prior art.
  • Another advantage is the more uniform curing of the three-dimensionally shaped component.
  • the thermally deformable plate can be deformed with a protective film, which is not possible with conventional dual-cure systems because it is only physically crosslinked. This is the surface in the manufacturing process and further Processing steps or during transport additionally protected. Thermoforming is possible on conventional systems. After the first component has hardened (and before the second component has hardened), the top coat surface is dry to the touch, stackable and stable in storage.
  • the lacquer layer is elastic and stretchable.
  • composition of the paint comprises a mixture of the components summarized in Table 1: Table 1: Composition of the lacquer of the lacquer top layer: component Weight% description 1 Urethane (meth) acrylate oligomer 35 Laromer® UA 9072 2 1,6 hexanediol diacrylate 10 Reactive thinner 3 2,4,6-trimethylbenzoyldiphenylphosphine oxide 3 Ciba® Darocur®TPO photoinitiator 4th Isocyanate 25th Isophorone diisocyanate 5 Polyol 24 Terol 250® 6th 3,5-dimethylpyrazole 2 Blocking agents 7th Dibutyltin dilaurate (DBTL) 1 Master ZI 4401 catalyst
  • the components 1 to 3 of the paint according to Table 1 form the first component with an acrylic component.
  • Components 1 to 3 were cured by means of UV light and the resulting component is thermoplastically deformable after curing.
  • the mixture of components 4 to 7 forms the second part of the top coat of paint. These components are cured in a second step.
  • properties of the lacquer top layer after curing of the first component ("before deformation") and after curing of the second component by means of thermal treatment by thermoforming were examined.
  • the thermoforming temperature is 180 ° C.
  • Table 2 Examination of the paint layer after curing of the first component and before or after curing of the second component.
  • Fig. 1 shows schematically the thermally deformable plate of the example in cross section, comprising a cover layer 1 and a thermoplastic plastic plate, which comprises a total of five layers 2, 3, 4, 5, 6.
  • the substrate layer 5 takes up the main part.
  • the remaining layers 2, 3, 4, 6 can contribute additional mechanical and / or optical properties.
  • a protective film 10 is indicated on the surface of the lacquer cover layer 1.
  • the plastic film or sheet does not, of course, have to contain 5 layers, it can also have only one or two or more layers, for example.
  • Fig. 2 shows FT-IR spectra of the lacquer top layer 1 according to the invention.
  • the solid line shows the top coat of paint after the paint has been applied and the first component (acrylic components 1 to 3 in the example shown) has hardened onto the plastic plate. This plate was then predried at 70 ° C. for 24 hours in order to remove the residual moisture from the plastic plate.
  • the FT-IR spectrum of the top coat of paint is shown dotted. The difference to the measurement before storage at 70 ° C / 24 hours is small.
  • the FT-IR spectrum changes significantly, in particular the transmission of the characteristic band at around 900 cm .1 becomes significantly higher.
  • the physico-chemical properties of the surface of the top coat of paint after curing of the second component improved significantly. It was surprising that thermal curing as the final curing step of a top coat of paint for plastics produced the same surface quality (physically and chemically) as UV curing as the final step. With the thermal curing of lacquers on plastics, it has traditionally never been possible to achieve such results.

Claims (10)

  1. Plaque ou feuille thermo-déformable comprenant une plaque de plastique ou une feuille de plastique thermoplastique (2, 3) et une couche de revêtement en vernis (1) dotée d'au moins deux constituants, dans laquelle la couche de revêtement en vernis (1) possède comme premier constituant un composant thermo-formable déjà durci et comme deuxième constituant un composant thermodurcissable, caractérisée en ce que le composant thermo-formable déjà durci est un composant durci par la lumière UV, le composant thermodurcissable étant choisi de telle sorte qu'il durcit à une température à laquelle la plaque de plastique ou la feuille de plastique thermoplastique (2, 3) est thermo-formable, la température à laquelle le composant thermodurcissable durcit étant située entre 140 et 210 °C, de préférence entre 160 et 190 °C et de façon particulièrement préférable entre 165 et 185 °C.
  2. Plaque ou feuille thermo-déformable selon la caractéristique 1, caractérisée en ce que la plaque de plastique ou la feuille de plastique thermoplastique (2, 3) est constituée d'une ou plusieurs couches et contient des matières thermoplastiques choisies parmi le groupe des polyoléfines, des polymères de styrène, du polycarbonate, des polyacrylates, du polyester, des élastomères thermoplastiques, des élastomères thermoplastiques à base d'oléfine ou du polyuréthane thermoplastique.
  3. Plaque ou feuille thermo-déformable selon la caractéristique 1 ou la caractéristique 2, caractérisée en ce que le composant thermo-formable déjà durci est un polymère qui peut être fabriqué à partir d'oligomères d'acrylate, de diluants réactifs et de photo-initiateurs.
  4. Plaque ou feuille thermo-déformable selon une des caractéristiques 1 à 3, caractérisée en ce que le composant thermodurcissable est fabriqué à partir d'isocyanates bloqués et de polyols.
  5. Plaque ou feuille thermo-déformable selon une des caractéristiques 1 à 4, caractérisée en ce que sur la couche de revêtement (3) est disposée une feuille de protection (4).
  6. Plaque ou feuille déformée comprenant une plaque ou une feuille selon une des revendications 1 à 5, dans laquelle les composants thermodurcissables sont durcis.
  7. Pièce comprenant une plaque thermoplastique selon la revendication 6.
  8. Pièce selon la revendication 7, caractérisée en ce que cette pièce est une pièce de carrosserie, une pièce sanitaire, une feuille pour meuble ou un boîtier.
  9. Procédé pour la fabrication d'une plaque de plastique ou d'une feuille de plastique thermo-déformable selon une des revendications 1 à 5, comprenant les étapes suivantes :
    (i) préparation d'une plaque de plastique ou d'une feuille de plastique thermoplastique (2, 3),
    (ii) application d'un vernis doté d'un premier constituant durcissable par lumière UV qui est thermo-déformable à l'état durci et d'une deuxième constituant thermodurcissable, le vernis étant appliqué à l'état liquide, et
    (iii) durcissement uniquement du premier constituant durcissable par la lumière UV,
    le vernis étant thermo-formable après le durcissement du premier constituant durcissable.
  10. Procédé pour la fabrication d'une plaque de plastique ou d'une feuille de plastique déformée selon la revendication 6, comprenant les étapes suivantes :
    (a) préparation d'une plaque ou d'une feuille thermo-déformable selon une des revendications 1 à 5 ou fabriquée dans un procédé selon la revendication 9 et
    (b) thermoformage de la plaque de plastique ou de la feuille de plastique dans une forme tridimensionnelle souhaitée avec durcissement simultané des composants thermodurcissables.
EP16194022.6A 2016-10-14 2016-10-14 Plaque thermo-déformable Active EP3308956B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP16194022.6A EP3308956B1 (fr) 2016-10-14 2016-10-14 Plaque thermo-déformable
ES16194022T ES2894109T3 (es) 2016-10-14 2016-10-14 Placa deformable térmicamente
RU2019114209A RU2745957C2 (ru) 2016-10-14 2017-10-13 Термически формуемые пластины
MX2019004313A MX2019004313A (es) 2016-10-14 2017-10-13 Placa deformable por accion termica.
CN201780063595.7A CN109843582B (zh) 2016-10-14 2017-10-13 可热变形的片材
JP2019520619A JP6871368B2 (ja) 2016-10-14 2017-10-13 熱変形可能なプレート
CA3039141A CA3039141A1 (fr) 2016-10-14 2017-10-13 Plaque a deformation thermique
US16/339,108 US20210283824A1 (en) 2016-10-14 2017-10-13 Thermally deformable plate
BR112019007442A BR112019007442A2 (pt) 2016-10-14 2017-10-13 placa deformável térmicamente
PCT/EP2017/076197 WO2018069502A1 (fr) 2016-10-14 2017-10-13 Plaque à déformation thermique
KR1020197010661A KR102268281B1 (ko) 2016-10-14 2017-10-13 열적으로 변형가능한 플레이트

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16194022.6A EP3308956B1 (fr) 2016-10-14 2016-10-14 Plaque thermo-déformable

Publications (2)

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EP3308956A1 EP3308956A1 (fr) 2018-04-18
EP3308956B1 true EP3308956B1 (fr) 2021-07-07

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EP16194022.6A Active EP3308956B1 (fr) 2016-10-14 2016-10-14 Plaque thermo-déformable

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US (1) US20210283824A1 (fr)
EP (1) EP3308956B1 (fr)
JP (1) JP6871368B2 (fr)
KR (1) KR102268281B1 (fr)
CN (1) CN109843582B (fr)
BR (1) BR112019007442A2 (fr)
CA (1) CA3039141A1 (fr)
ES (1) ES2894109T3 (fr)
MX (1) MX2019004313A (fr)
RU (1) RU2745957C2 (fr)
WO (1) WO2018069502A1 (fr)

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DE19860041A1 (de) * 1998-12-23 2000-06-29 Basf Ag Durch Addition an Isocyanatgruppen als auch durch strahlungsinduzierte Addition an aktivierte C-C-Doppelbindungen härtbare Beschichtungsmittel
DE19917965A1 (de) * 1999-04-21 2000-10-26 Daimler Chrysler Ag Strahlungshärtbare Verbundschichtplatte oder -folie
DE19938759A1 (de) * 1999-08-16 2001-02-22 Basf Coatings Ag Beschichtungsstoff und seine Verwendung zur Herstellung hochkratzfester mehrschichtiger Klarlackierungen
AT500082B1 (de) * 2003-10-31 2007-08-15 Senoplast Klepsch & Co Gmbh Mehrschichtiger verbundkörper und dessen herstellung
DE102004009437A1 (de) * 2004-02-24 2005-09-15 Basf Ag Strahlungshärtbare Verbundschichtplatte oder -folie
DE102004055363A1 (de) * 2004-04-16 2005-11-10 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg Flexibler Schichtverbund mit einem Träger und einer darauf angebrachten Schicht härtbaren Lackes
DE102010014381A1 (de) * 2010-04-01 2011-10-06 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg Substrate mit mehrfarbiger Lackierung und ihre Herstellung
JP6684779B2 (ja) * 2015-03-31 2020-04-22 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
US10538031B2 (en) * 2015-12-22 2020-01-21 Carbon, Inc. Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products

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Also Published As

Publication number Publication date
US20210283824A1 (en) 2021-09-16
CN109843582A (zh) 2019-06-04
ES2894109T3 (es) 2022-02-11
RU2745957C2 (ru) 2021-04-05
RU2019114209A (ru) 2020-11-16
EP3308956A1 (fr) 2018-04-18
JP6871368B2 (ja) 2021-05-12
WO2018069502A1 (fr) 2018-04-19
BR112019007442A2 (pt) 2019-07-09
MX2019004313A (es) 2019-11-12
KR20190069425A (ko) 2019-06-19
KR102268281B1 (ko) 2021-06-23
CA3039141A1 (fr) 2018-04-19
RU2019114209A3 (fr) 2020-11-16
CN109843582B (zh) 2021-09-03
JP2019531943A (ja) 2019-11-07

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